Mixed resin acid esters of 4, 4-bis(4-hydroxyaryl) pentanoic acid



United States Patent .j

MIXED RESIN ACID ESTERS OF 4,4-BIS(4 HYDROXYARYL) PENTANOIC ACID Sylvan 0. Greenlee, Racine, Wis., assignor to S. C. Johnson & Son, Inc., Racine, Wis.

No Drawing. Application June 30,1955 Serial No. 519,279

9 Claims. Cl. 260-24) This invention relates to new compositions which are mixed esters ofpolyhydric alcohols, natural resin,acids,

reaction products having unusually good chemical resistance, hardness, gloss, etc.

These and other objects and advantages are attained by the present invention, various novel features of which will become more fully apparent from the following description, with particularreference to specific examples which are to be considered as illustrative only.

The compositions of this invention, being esters of polyhydric alcohols and mixtures of natural resin acids and hydroxyaryl-substituted aliphatic acids, are relatively high molecular weight resinous polyhydric phenols. The number of phenolic groups per molecule. are dependent on the number of alcoholic hydroxyl groups present in the polyhydric alcohol esterified, as well as on the amounts and proportions of natural resin acid and hydroxyaryl-substituted aliphatic acid used in the preparation of the esterified product.

The mixed esters of this invention combine within the same chemical molecule natural resin acid esters and a phenolic residue, the natural resin acid ester portion being similar to the natural resin acid portion presentin the so-called ester gums which are natural resin acid esters of polyhydric alcohols. This property renders the compositions of this invention particularly valuable in the manufacture of complex products such as coating and molding compositions, where the natural resin acid esters are desirable for the purpose of contributing hardness and gloss to the finished product. The phenolic residues present in the compositions and introduced by the hydroxyaryl-substituted aliphatic acids contribute reactive phenolic hydroxyl groups which for the most part do not enter into the esterification reaction used in the preparation of the mixed esters of this invention. These functional groups permit further reaction between the mixed esters of this invention and such materials as aldehydes, epoxides, and carboxylic acids to yield additional complex products. Reaction with aldehydes, either in' the presence or absence of other compounds capable of polymerization with aldehydes, gives compositions which are valuable constituents of protective coatings and molding resins. Similarly, the phenolic hydroxyl groups of the phenolic residues may be reacted with polyepoxide compositions to give highly polymerized products containing within the same molecule the natural resin acid esterresidues. Esterification of the phenolic hydroxyl groups of the phenolic residue with dibasic acids would also give polymerization in which the natural resin acid ester becomes an intimate part of the final polymer chemical composition. Such esterification reactions involving the phenolic hydroxyl groups would conveniently be carried out by heating with a mixture of the dibasic acid and acetic anhydride.

The hydroxyarylsubstituted aliphatic acids contemplated for use in preparing the desired resinous polyhydric phenols have two hydroxyphenyl groups attached to a single carbon atom. The preparation of these substituted acids may be most conveniently carried out by condensing a keto-acid with the desired phenol. Experience in the preparation of bisphenols and related compounds indicates that the carbonyl group of the ketoacid must be located next to a terminal carbon atom in order to obtain satisfactory yields. A terminal carbon atom as used herein refers to primary carbon atoms other than the carboxyl carbon atom of the keto-acid. Prior applications, Serial Nos. 464,607 and 489,300, filed October 25, 1954, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the hydroxyaryl-substituted acid, and methods of preparing'the same. These materials, which are referred to for convenience as Diphenolic Acid, or DPA a trademark of S. C. Johnson & Son, Inc., comprise the condensation products of levulinic acid and phenol, substituted phenols or mixtures thereof. It is to be understood that the phenolic nuclei of the Diphenolic Acid may be substituted with any groups which will not interfere with the esterification reactions. For example, the nuclei may be alkylated as disclosed in Serial No. 489,300 or they may be halogenated. The Diphenolic Acid derived from 1 mol of levulinic acid and 2 mols of phenol is particularly advantageous in that it may be readily prepared to a high degree of purity, whereas the use of substituted phenols, such as the alkylated products, usually results in. mixed compositions which are less readily purified. On the other hand, there are cases Where the Diphenolic Acid derived from alkylated phenols are more desirable than those derived from the nonalkylated product on the basis that the alkyl groups tend to give better organic solvent solubility, flexibility, and better water resistance.

The natural resin acids which may be used with these hydroxyaryl-substituted acids in the co-esterification of the polyhydric alcohols are illustrated by the commercial grades of rosin and other natural-occurring acid resins, such as the kauri, copal, damar, and Congo gums. Typical commercial grades of rosin, for example, have acid values of, around 150-175. Acid values as used herein are defined as the number of milligrams of KOH required to neutralized the acid present in a one-gram sample. Typical damar gums have acid values ranging from 18 to 60. Kauri gums have acid values of from 60-80, while copal gums have acid values in the range of -130. The essential composition or" all these natural-occurring resin acids are cyclic terpenic type acids of which abietic acid is fairly typical.

The polyhydric alcohols may be the nonresinous type or the resinous type. These polyhydric alcohols, because of their polyfunctionality, will esterify with natural resin acids and hydroxyaryl-substituted acids to give a resinous phenolic product. Illustrative of the nonresinous type polyhydric alcohols are such materials as ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, 1,3-butane diol, 2,5-pentane diol, 1,6-hexane diol, neopentyl glycol, glycerol, erythritol, pentaerythritol, polypentaerythritols, sorbitol, mannitol, alpha methyl glucoside, polyallyl alcohols, diethanolamine, triethanolamine, and tetramethylol cyclohexanol The resinous p y y alcohols Which y be used Esterifieation of either the nonresinous or resinous in the preparation of the subject esters may be illustrated polyhydric l h l with Di henoli A id and natural y Such materials as the l'esinells Ieaetion Products of resin acids is conveniently carried out by direct heating st e v yp nyl) p py With ethylene ch10 at temperatures of from 190275 C. under conditions Tohydriil g y mofieehlofohydrin- The reaction 5 where the water produced during condensation is continuef the Same. dihydrie Phenol with epichlorohydfln or ously removed as it is formed. In the case where epl i' 'die'hlofohydfin gives resinous p y y a100- oxide groups of, for example, a resinous composition of H015 which Polymeric p y y alcohols and Which the Epon resin type produced by Shell Chemical Corpoin some cases. addition to the alcholic y y p ration are partially esterified only to the, extent of one 'eollt'ain ePOXide p epoxidereenwinihg P carboxyl group reacting with one epoxide group, lower nets are 'well illustrated by the commercially availa le temperatures may b d d no ater i formed since Epon resins marketed y Shell Chemical Corporation) the reaction of the carboxyl group with the epoxide The preparation of these resinous p y y alcohols are group is that of direct addition with the formation of an described in US. Patents 2,456,408, 2,503,726, 2,615,008, ester-linkage and a free hydroxyl group. Since the Di- '2,6'68,805, 2,668,807 an 2693,315- phenolic Acid and the polyhydric alcohols have boiling Other resinous p y y which y be points which are in all cases above 190 C., the Water ployed may be illustrated by those which are prepared b r d by rmitti itto olatilize during esby the'reaction of phenol-formaldehydecondensates with teriiication, Rgmoval f thelwam-vmayp also-be fadchlorohydrins. For example, analkylphenol m y b Contated by continuously bubblin gthrough the reaction mixdells'ed With formaldehyde, followed y treatment of 8m ture during esterification a stream of inert gas, such as alkaline solution of this intermediate methylol derivative carbon di id nitrogen, It is al o sometimes conven- With chlerohydrln, Such as glycerol'mollqehlorohydfini lent to. facilitate the water removal bycarrying out the to y d after condensation a Polymeric p y y aleoreaction in a vessel provided. with condenser attached 'hol. This resinous polyhydric alcohol may then be'used thereto through a water trap, adding a suflicient amount in esterification with the diphenolic acids to prepare the of a volatile, water-insoluble. solvent to give reflux at the subject resinous polyhydric phenols; esterification temperature, continually removing the wa- A yp formula for a p i n r n descri ter by azeotropic distillation and permitting the solvent may be illustrated by the following reaction between equal to return to the reaction mixture after having dropped the molar portions of ethylene glycol, abietic acid, and 4,4- water in the water trap. V bis(4-hydroxyphenyl)pentanoic acid. Abietic acid is the The order of addition of the various ingredients, Di- "chief acid ingredient of commercial rosin and is typical phenolic Acid, resin acids, and polyhydric alcohols, to of the terpenic type acids present in the natural resin each other may be varied. It is sometimes advantageous acids. to vary this order of addition to obtain optimum results H3O GOZH HOG onioniooin H 0 0 V on OH OH heat C +l 1 ll a A g on on,

CH3 0 on,

H: no onioniooionionioio on CHzOH H1O C I' ("JH on HiiG 0-0 a C s a From the above formula it will be obvious that use of with the particular combination of ingredients used. In more complex polyhydric alcohols, such as glycerol, the art of high temperature esterification, it is sometimes pentaerythritol, and the polypentaerythritols, would give advantageous to use certain esterification catalysts, and higher molecular weight products in which the ratio of these'may be used in the preparation of the compositions Diphenolic Acid to natural resin acid may be varied of this invention.

through wide ranges. It is understood that the composi- The following examples will serve to illustrate this intions obtained by co-esterification of polyhydric 'alcovention, however, 'it should be understood that the inhols with Diphenolic Acid and the natural resin acids vention. is not intended to be limited thereby; In'the give mixed products, including to some extent esterificaexamples, proportions expressed are parts by weight un tion of the phenolic hydroxyl groups of Diphenolic Acid less otherwise indicated. i

with the carboxyl groups of diphenolic acid itself as well Examples I to VI illustrate the preparation of some as esterification of the alcoholic 'hydroxyl groups by the polyhydric alcohol esters of inixturesof Diphenolic'Acid natural resin acids. For the most part, however, the more 7 and-natural resin acid esters. These reactions are in all reactive alcoholic hydroxyl groups of the polyhydric al cases carried out in vessels provided with a thermometer, 'cohols tend-to-esterify to a greater extent than the phenola mechanical agitator, and a condenser attached through ydroxyl groups. These compositions are valuable in a water trap. Inert gas was bubbled through the reacform'ulating useful products in the coat ngs, molding, tion mixtures throughout esterification so as to remove and adhesive field. l water formed in the esterification.

Example 11 A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 34 parts of ethylene glycol was esterified to an acid value of 7 yielding a product having a softening point of 81 C.

Example III In a reaction vessel provided with a mechanical agitator was placed 452 parts of bis(4-hydroxyphenyl)isopropylidene dissolved in 1500 parts of water containing 82 parts of sodium hydroxide. The temperature of the continuously agitated solution was raised to 60 C. and 93 parts of epichlorohydrin was added slowly at 60-65 C. After addition of the epichlorohydrin was complete, the temperature was gradually raised to 95 C. and held at this temperature for a period of 1 hour. A solution of 82 parts of sodium hydroxide dissolved in 500 cc. of

water was added, lowering the temperature to 73 C. at which point 161 parts of ethylene chlorohydrin was added slowly over a period of 28 minutes. After all of the ethylene chlorohydrin had been added, the temperature was gradually raised to 95 C. and held for 1 hour. The unreacted caustic was neutralized by adding 100 parts of 37% aqueous HCl and the product was washed several times with hot water to remove the salt and excess HC]. The product was finally dried by heating with agitation giving 558 parts of a product having a softening point of 56 C.

To the 558 parts of this polymeric polyhydric alcohol was added 360 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and 415 parts of a commercial grade of rosin having an acid value of 160, and the resulting mixture esterified to an acid value of 6.4. The product had a softening point of 102 C.

Example IV A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 37 parts of pentaerythritol was esterified to an acid value of 7.5 to yield a product having a melting point of 126 C.

Example V Example VI A mixture of 174 parts of Epon 1004 and 101 parts of commercial rosin was esterified to an acid value of 19 at which point 86 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid was added and esterification continued until an acid value of 139 was reached, giving a product having a softening point of 131 C. I

The remaining examples illustrate the preparation of more complex products by the reaction of the mixed esters of this invention with formaldehyde, to produce a resinone composition useful in the manufacture of protective coatings; It will be understood, of course, that the phenolic hydroxyl groups of themixed esters may be reacted with other materialssuch as epoxides or other acids, to give various other reaction products. These products generally possess the hardness and ,gloss characteristic of natural resin esters and show other exceptional properties such as flexibility, chemical resistancaetc.

Example VII A mixture of parts of the resinous product of Example I, 21 parts of 38% aqueous formaldehyde, .063 part of oxalic acid and 17 parts of xylol was heated with continuous agitation for a period of 1 hour and 30 minutes at 95 C., after which the water layer was removed by decantation. The organic resin layer was heated with agitation to C. at a reduced pressure of around 30-40 mm. in order to remove the last traces of water.

A mixture of 10 parts of this formaldehyde reaction product and 10 parts of linseed oil was heated with agitation for 30 minutes at 240-280 C. at which point 10 parts of China-wood oil was added and agitation continued until the mixture had cooled to 228 C., and this temperature held for 15 minutes. This product was dissolved to 50% nonvolatile content in a solvent composed of equal weights of xylol and a high boiling naphtha (boiling range -225 C. and an aniline point of 60 C. to a viscosity of A-3 Gardner-Holdt bubble viscometer). This varnish was treated with 03% cobalt naphthenate drier and 3% lead naphthenate drier based on Example VIII Replacing the resinous product of Example I with the resinous product of Example II in the reaction with formaldehyde, and final cooking with the drying oils, as in Example VII, gave a product which formed flexible air-dried films which withstood boiling water for a period of 1 hour.

The mixed esters of this invention may be modified to some extent by incorporating with the esters other constituents. These constituents maybe inert constituents such as fillers, pigments, or certain plasticizers, or they may contain functional groups and enter into the esterification of the polyhydric alcohols with natural resin acids and hydroxyaryl-substituted acids so as to be chemically carried by the mixed esters of this invention.

It should be appreciated that while there are above disclosed only a limited number of embodiments of this invention, it is not intended to be restricted thereto, and that it is intended to cover all modifications of the invention which would be apparent to one skilled in the art and that come within the scope of the appended claims.

It is claimed and desired to secure by Letters Patent:

1. A new composition of matter comprising the mixed ester of a fusible polyhydric alcohol, a natural resin acid, and a pentanoic acid consisting essentially of 4,4 bis(4- hydroxyaryl) pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms.

2. The composition of claim 1 where the pentanoic acid consists essentially of 4,4 bis(4-hy-droxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.

3. The composition of claim 1 wherein the pentanoic acid is 4,4 bis(4-hydroxyphenyl)pentanoicacid.

4. The composition of claim 3 wherein the natural resin acid is rosin.

. 5. The composition "of clai1nwhefe in the natuial resin acid. is abietic acid 7 Q V v A 6. The composition-ofclaimj wherein the polyhydiiic alcohol is a polyglycidyl ther of a member of the group consisting of polyhydr ic phenols and polyhydric alcohols. 7. The composition of claim. 3- wherein-the polyhydric alcohol is.g1'yce '-ol.

8. The composition of claim 3 'wherein the polyhydric alcohol 'is ethylene glycol.

9-. The coinp'ositionbf -clgirn 3 wherein the polyhydric alcohol is pntaerythritbl; I

7 No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,907,738

October 6, I959 Sylvan 0. Greenlee It is hereby certified that err of the above numbered patent requiri or appears in the-printed specification Patent should ng correction and that the said Letters read as corrected below. Column 2, line 52, for "neutralized" read neutralize column 3, line 25, for "diphenolic acids" read Diphenolic Acid line 68, for "d' iphenolic acid" read Diphenolic Acid Signed and sealed thia 14th day of June 1960.

(SEAL) Attest: KARL "I1. AXLINE ROBERT C. WATSON \ttesting Officer Commissioner of Patents 

1. A NEW COMPOSITION OF MATTER COMPRISING THE MIXED ESTER OF A FUSIBLE POLYHYDRIC ALCOHOL, A NATURAL RESIN ACID, AND A PENTANOIC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4HYDROXYARYL) PENTANOIC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RAIDCAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS. 